Calculation of chemical-shift tensors of heavy nuclei: a DFT/ZORA investigation of 199Hg chemical-shift tensors in solids, and the effects of cluster size and electronic-state approximations
| Author(s) | Alkan, Fahri | |
| Author(s) | Dybowski, Cecil | |
| Ordered Author | Fahri Alkan and C. Dybowski | |
| UD Author | Alkan, Fahri | en_US |
| UD Author | Dybowski, C. | en_US |
| Date Accessioned | 2016-03-16T14:38:51Z | |
| Date Available | 2016-03-16T14:38:51Z | |
| Copyright Date | Copyright © the Owner Societies 2014. | en_US |
| Publication Date | 2014-06-02 | |
| Description | Publisher's PDF | en_US |
| Abstract | Calculations of the nuclear magnetic resonance chemical-shielding tensors of a suite of mercury-containing materials using various cluster models for the structures provide a stringent test of the procedures for forming models and for calculation with various methods. The inclusion of higher co-ordination shells in the molecular clusters permits quantum chemical calculations of 199Hg chemical-shielding tensor elements within 3% of the experimental values. We show that it is possible to reduce the size of computationally expensive molecular-cluster calculations with limited effect on calculated NMR parameters by carefully introducing the frozen core approximation. The importance of the relativistic Hamiltonian for accurate predictions of chemical-shielding values is demonstrated within the molecular cluster approach. The results demonstrate that careful design of a cluster to represent the solid-state structure, inclusion of relativistic components in the Hamiltonian at least at the spin–orbit level, and judicious use of approximations are essential to obtain good agreement with experimental results. | en_US |
| Department | University of Delaware. Department of Chemistry and Biochemistry. | en_US |
| Citation | Alkan, Fahri, and Cecil Dybowski. "Calculation of chemical-shift tensors of heavy nuclei: a DFT/ZORA investigation of 199 Hg chemical-shift tensors in solids, and the effects of cluster size and electronic-state approximations." Physical Chemistry Chemical Physics 16.27 (2014): 14298-14308. | en_US |
| DOI | DOI: 10.1039/C4CP01682C | en_US |
| ISSN | 1463-9076 ; e- 1463-9084 | en_US |
| URL | http://udspace.udel.edu/handle/19716/17508 | |
| Language | en_US | en_US |
| Publisher | Royal Society of Chemistry | en_US |
| dc.rights | CC-BY 3.0 https://creativecommons.org/licenses/by-sa/3.0/us/ Authors retain copyright. | en_US |
| dc.source | Physical Chemistry Chemical Physics | en_US |
| dc.source.uri | http://pubs.rsc.org/en/journals/journalissues/cp#!recentarticles&adv | en_US |
| Title | Calculation of chemical-shift tensors of heavy nuclei: a DFT/ZORA investigation of 199Hg chemical-shift tensors in solids, and the effects of cluster size and electronic-state approximations | en_US |
| Type | Article | en_US |
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